Abstract The distillation of azeotropic mixtures is commonly and widely performed in the pharmaceutical, petroleum, and chemical industries. Deep eutectic solvents (DESs) are environmentally-friendly entrainers that have many properties similar to ionic liquids (ILs) but are also simple in preparation and cheap in price. Also, the ethanol/water system is a typical industrial azeotropic mixture. In this work, the relative volatility of ethanol and water at the azeotropic point was increased from 1.00 to 4.70 with 0–51.0 mass % ChCl/urea (1:2, mol/mol), with ChCl/urea showing a remarkable entrainer performance in this separation. Isobaric vapor–liquid equilibrium (VLE) data of four systems, water + ethanol, water + ChCl/urea, ethanol + ChCl/urea, and water + ethanol + ChCl/urea (at 10, 20, and 30 mass%), were determined using a modified Othmer equilibrium still at 101.32 kPa. After addition of ChCl/urea, the ethanol + water mixture’s azeotropic point was eliminated. The parameters of the nonrandom two-liquid (NRTL) model for these systems were calculated and the predicted values for these systems were found to fit the experimental VLE data quite well.